CN104240970A - Method for preparing alpha-nickel sulfide and carbon nanometer rodlike composite material in in-situ mode - Google Patents
Method for preparing alpha-nickel sulfide and carbon nanometer rodlike composite material in in-situ mode Download PDFInfo
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- CN104240970A CN104240970A CN201410354191.1A CN201410354191A CN104240970A CN 104240970 A CN104240970 A CN 104240970A CN 201410354191 A CN201410354191 A CN 201410354191A CN 104240970 A CN104240970 A CN 104240970A
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Abstract
The invention discloses a method for preparing an alpha-nickel sulfide and carbon nanometer rodlike composite material in an in-situ mode. The method is mainly characterized in that the method that nanometer rodlike carbon wraps nickel in an in-situ backflow vulcanizing mode is adopted to prepare the alpha-nickel sulfide and carbon nanometer rodlike composite material, and controllable adjusting on the nickel sulfide crystalline phase is achieved through the nanometer limited range action of a carbon nanometer rod . Compared with the existing synthetic technology, according to the alpha-nickel sulfide and carbon nanometer rodlike composite material synthesized through the method, the crystalline phase of the alpha-nickel sulfide is single, the alpha-nickel sulfide is distributed evenly in the carbon nanometer rod, the synthesis process is simple, repeatability is good, and a supercapacitor electrode made of the nanometer composite material has a large specific capacitance value and good circulation stability.
Description
Technical field
The present invention relates to a kind of method utilizing solvent-thermal method original position to prepare the nano bar-shape composite material of α-nickel sulfide and carbon.
Background technology
Metal sulfide is as FeS
2, CoS
x, MoS
2with NiS etc. owing to having higher theoretical capacity, it is potential electrode material for super capacitor.NiS aboundresources, low toxicity, conductivity is better, receives the extensive concern of researchers in recent years.But NiS change in volume in charge and discharge process is comparatively large, easily causes condenser capacity rapid decay.At present, much research is all attempted improving its chemical property by various method, and as ball-milling method reduces particle size, liquid phase synthesizing method or pattern are modified and controlled its granule-morphology etc.The another kind of method effectively improving metal sulfide electrical property forms compound, as Co with basis material
9the compound features of S and carbon goes out superior electrical property.
Material with carbon element is due to its electrical conductance excellence, and specific area is large, and mechanical strength is high, is the desired matrix of electrochemical active material.Nearest research also shows, carbon-based nano composite material as NiO/ Graphene, MoS
2/ Graphene and Ni
3s
2/ carbon nano-tube etc. all show superior chemical property.Why carbon nanomaterial significantly can improve the chemical property of sulfide, not only because it effectively can suppress the change in volume of metal sulfide in charge and discharge process, electrochemical active material can also be made in long cyclic process to keep good dispersiveness.In addition, as conductive frame, carbon nanomaterial effectively can maintain it and active material and the conductive channel between active material and current-collector, makes C-base composte material show higher ratio capacitance value and excellent cyclical stability.
The invention discloses a kind of method that original position prepares the nano bar-shape composite material of the controlled α-nickel sulfide of crystalline phase and carbon, the existence of nano bar-shape carbon can not only make generation α-nickel sulfide crystalline phase is single, nanoparticulate dispersed is even, the expansion of the volume of nickel sulfide can also be stoped in the process of charge and discharge cycles, improve its chemical property.
Summary of the invention
The object of this invention is to provide a kind of method utilizing original position circumfluence method to prepare the α-nickel sulfide of single crystalline phase and the nano bar-shape composite material of carbon.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for the nano bar-shape composite material of α-nickel sulfide that crystalline phase is controlled and carbon, the method mainly adopts the method for nano bar-shape carbon-coating nickel original position backflow sulfuration to prepare the composite material of α-nickel sulfide and carbon nano rod.The method of described original position backflow sulfuration is specially: nano bar-shape carbon-coating nickel is added hot reflux 0.8 ~ 2.0 hour in the glycerol containing sulphur source.In the composite, α-nickel sulfide is the nano particle be evenly distributed, and α-nickel sulfide crystalline phase is single.
Described sulphur source is the one of thiocarbamide, thioacetamide or glutathione.
The mass ratio in nano bar-shape carbon-coating nickel and sulphur source is 1:1 ~ 15, and preferred mass is than being 1:3 ~ 15.
In glycerol containing sulphur source, the mass ratio of sulphur source and glycerol is 1:100 ~ 1000.
Described nano bar-shape carbon-coating nickel is prepared by nickel dimethylglyoximate high-temperature calcination in argon atmospher.High-temperature calcination temperature is 300 ~ 600 DEG C, and the high-temperature calcination time is 1 ~ 3 hour.
Complexing after dimethylglyoxime and nickel chloride mixing can prepare by described nickel dimethylglyoximate, also can be prepared according to prior art.
The concrete steps of the nano bar-shape composite material and preparation method thereof of the controlled α-nickel sulfide of above-mentioned crystalline phase and carbon are:
Nickel dimethylglyoximate high-temperature calcination in argon atmospher is obtained nano bar-shape carbon-coating nickel composite material, nano bar-shape carbon-coating nickel composite material is added hot reflux 0.8 ~ 2.0 hour in the glycerol containing sulphur source, generate α-nickel sulfide and carbon nano rod composite material.
The product that the inventive method generates is the α-nickel sulfide of single crystalline phase and the nano composite material of carbon, simply saves time, is easy to operate, morphology controllable compared with conventional hydrothermal synthetic method.
Described α-nickel sulfide and the nano bar-shape composite material of carbon can be used as electrode material for super capacitor and have good super capacitor characteristics.
Compared with existing nickel sulfide synthetic technology, the invention has the advantages that:
1), the method for the nano bar-shape composite material of the first public a kind of original position crystalline phase controlled synthesis α-nickel sulfide of the present invention and carbon, the method can obtain the nano bar-shape composite material of α-nickel sulfide and carbon by the original position sulfuration nano bar-shape carbon-coating nickel that refluxes, preparation technology is simple, product morphology is controlled, cheap, be easy to realize scale preparation;
2), in the preparation method of the nano bar-shape composite material of α-nickel sulfide disclosed in this invention and carbon, nickel sulfide crystalline phase is single, and has the controlled characteristic of crystalline phase;
3) α-nickel sulfide, prepared by the present invention and the nano bar-shape composite material of carbon, nickel sulfide can be uniformly dispersed in carbon base body;
4) α-nickel sulfide, prepared by the present invention and the nano bar-shape composite material of carbon can be used as high-performance super capacitor electrode material.
5), the present invention adopts the coated nickel of carbon nano rod to be template, makes the α-nickel sulfide of generation be dispersed in carbon nano rod, effectively can stop the particle agglomeration in charge and discharge process, improves the cyclical stability of electrode.Carbon nano rod can the high α-nickel sulfide of the single conductivity of controlled generation to the coating function of nickel sulfide, and to lose the coated nickel of carbon reflux product be under the same conditions β-nickel sulfide.
Accompanying drawing explanation
Fig. 1. the nickel dimethylglyoximate (a) that the nano bar-shape composite material preparing α-nickel sulfide and carbon for embodiment 1 situ adopts in testing and the scanning electron microscopic picture of nano bar-shape carbon-coating nickel (b) obtained after calcining.
Fig. 2. the ESEM (a) of the α-nickel sulfide prepared for embodiment 2 situ and the nano bar-shape composite material of carbon and XRD (b) picture.
Fig. 3. in embodiment 3, under the existence without nano bar-shape carbon-coating nickel, the ESEM (a) of the composite material of β-nickel sulfide that bar-shaped carbon and nano metal nickel backflow sulfuration obtain and carbon and XRD (b) picture.
Fig. 4. XRD (b) picture of the mixture of Ni and the α-NiS obtained is tested for embodiment 5.
Fig. 5. XRD (b) picture of the α-nickel sulfide prepared for embodiment 6 situ and the nano bar-shape composite material of carbon.
Fig. 6. the nano bar-shape composite material of the α-nickel sulfide prepared for embodiment 8 situ and carbon is as the charging and discharging curve of electrode material for super capacitor under different current density and cyclical stability.
Embodiment
Below in conjunction with accompanying drawing and instantiation, the present invention is described in detail.
Embodiment 1:
0.3g dimethylglyoxime is dispersed in 30 milliliters of absolute ethyl alcohols, with the NaOH ethanolic solution of 0.5mol/L, dimethylglyoxime solution ph is adjusted to 13.0.0.3g nickel chloride is dissolved in 800mL water, under ultrasonic condition, dimethylglyoxime dropwise is added in the solution of nickel chloride, obtain red flocculent substance.By above-mentioned red fluffy solid suction filtration, washing, drying, its stereoscan photograph is as shown in Fig. 1 (a); By above-mentioned powder 500 DEG C of calcining 1h under Ar atmosphere, obtain black powder, i.e. nano bar-shape carbon-coating nickel, its stereoscan photograph is as shown in Fig. 1 (b).
Embodiment 2:
5 milligrams of nano bar-shape carbon-coating nickels (preparing according to embodiment 1 method) join ultrasonic disperse in 50 grams of glycerin solution, then 75 milligrams of thiocarbamides are added, stir backflow 1 hour, after naturally cooling to room temperature, obtain α-nickel sulfide and carbon nano rod compound after centrifugation, washing, its ESEM and XRD picture are as shown in Fig. 2 (a) He (b).
Embodiment 3:
Under the existence without nano bar-shape carbon-coating nickel, 2.5 milligrams of bar-shaped carbon and 2.5 milligrams of nano nickle granules join ultrasonic disperse in 50 grams of glycerin solution, reflux 0.8 hour in two mouthfuls of flasks after stirring, after naturally cooling to room temperature, centrifugation, carbon nano rod and the β-nickel sulphide particles of reunion is obtained after washing, its ESEM and XRD picture are as shown in Fig. 3 (a) He (b), this result proves that nano bar-shape carbon-coating nickel of the present invention has good nanometer confinement effect to product crystalline phase in backflow sulfidation, thus obtain the nano bar-shape composite material of the single α-nickel sulfide of crystalline phase and carbon.
Embodiment 4:
20 milligrams of nano bar-shape carbon-coating nickels (preparing according to embodiment 1 method) join ultrasonic disperse in 100 grams of glycerol, then 75 milligrams of thiocarbamides are added, stir backflow 2 hours, after naturally cooling to room temperature, the nano bar-shape composite material of homogeneous phase α-nickel sulfide and carbon after centrifugation, washing, can be obtained.
Embodiment 5
10 milligrams of nano bar-shape carbon-coating nickels (preparing according to embodiment 1 method) join ultrasonic disperse in 100 grams of ethylene glycol, then 100 milligrams of thiocarbamides are added, stir, reflux 2 hours, after naturally cooling to room temperature, what obtain after centrifugation, washing is the mixture of Ni and α-NiS, instead of the nano bar-shape composite material of the single α-nickel sulfide of crystalline phase and carbon is electrode material, illustrate that ethylene glycol solution is unfavorable for the generation of α-nickel sulfide, its XRD result as shown in Figure 4.
Embodiment 6:
50 milligrams of nano bar-shape carbon-coating nickels (preparing according to embodiment 1 method) join ultrasonic disperse in 150 grams of glycerol, then 150 milligrams of thioacetamides are added, stir backflow 2 hours, after naturally cooling to room temperature, can obtain the nano bar-shape composite material of homogeneous phase α-nickel sulfide and carbon after centrifugation, washing, its XRD result as shown in Figure 5.
Embodiment 7:
10 milligrams of nano bar-shape carbon-coating nickels (preparing according to embodiment 1 method) join ultrasonic disperse in 100 grams of glycerin solution, then 50 milligrams of glutathione are added, stir backflow 1 hour, after naturally cooling to room temperature, the nano bar-shape composite material of homogeneous phase α-nickel sulfide and carbon after centrifugation, washing, can be obtained.
Embodiment 8:
With the nano bar-shape composite material of the α-nickel sulfide obtained in embodiment 2 and carbon for electrode material, the potassium hydroxide of 2.0mol/L, as electrolyte, is 1.0,2.0,5.0,10.0A g in current density
-1time, initial discharge capacity can reach 1092,894,835,740F g
-1.After 2000 circulations, ratio capacitance is without obvious decline, and α-nickel sulfide is shown in Fig. 6 (a), 5.0A g from the charging and discharging curve of carbon nano rod shape electrode material under different current density
-1curve through 2000 charge and discharge cycles is shown in Fig. 6 (b).The present invention obtain α-nickel sulfide and carbon nano bar-shape composite material and other nickel sulfides and compound electrode material compared with, there is higher ratio capacitance and good cycle performance, as shown in table 1.
Table 1
Claims (9)
1. a preparation method for the nano bar-shape composite material of α-nickel sulfide and carbon, is characterized in that the method mainly adopts the method for nano bar-shape carbon-coating nickel original position backflow sulfuration to prepare the composite material of α-nickel sulfide and carbon nano rod.
2. method according to claim 1, is characterized in that the method for described original position backflow sulfuration is specially: nano bar-shape carbon-coating nickel is added hot reflux 0.8 ~ 2.0 hour in the glycerol containing sulphur source.
3. method according to claim 2, is characterized in that described sulphur source is the one of thiocarbamide, thioacetamide or glutathione.
4. method according to claim 2, is characterized in that the mass ratio in nano bar-shape carbon-coating nickel and sulphur source is 1:1 ~ 15.
5. method according to claim 2, is characterized in that the mass ratio of sulphur source and glycerol is 1:100 ~ 1000.
6. method according to claim 1, is characterized in that described nano bar-shape carbon-coating nickel is prepared by nickel dimethylglyoximate high-temperature calcination in argon atmospher.
7. method according to claim 6, is characterized in that described high-temperature calcination temperature is 300 ~ 600 DEG C, argon gas atmosphere.
8. method according to claim 6, is characterized in that the described high-temperature calcination time is 1 ~ 3 hour.
9. method according to claim 6, is characterized in that described nickel dimethylglyoximate is prepared complexing after dimethylglyoxime and nickel chloride mixing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807404A (en) * | 2017-02-07 | 2017-06-09 | 合肥工业大学 | A kind of preparation method and applications of base metal base carbon coating nickel sulfide photochemical catalyst |
| CN108390044A (en) * | 2018-03-08 | 2018-08-10 | 湖南大学 | A kind of curing nickel-carbon composite and its preparation method and application |
| CN108597893A (en) * | 2018-05-28 | 2018-09-28 | 江苏大学 | A kind of preparation method based on the composite electrode material for super capacitor in nickel foam |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127060A (en) * | 1998-06-17 | 2000-10-03 | Aer Energy Resources, Inc. | Recharge catalyst with thin film low corrosion coating, metal-air electrode including said catalyst and methods for making said catalyst and electrode |
| CN101049924A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for producing Nano carbon tube clad by metallic sulfide |
| US20080158778A1 (en) * | 1999-06-11 | 2008-07-03 | Lipka Stephen M | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| CN102760877A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Transition metal sulfide/graphene composite material, and preparation method and application thereof |
| CN102903541A (en) * | 2012-10-16 | 2013-01-30 | 湖南大学 | Method for preparing graphene-based electrode material for super-capacitor |
-
2014
- 2014-07-23 CN CN201410354191.1A patent/CN104240970B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127060A (en) * | 1998-06-17 | 2000-10-03 | Aer Energy Resources, Inc. | Recharge catalyst with thin film low corrosion coating, metal-air electrode including said catalyst and methods for making said catalyst and electrode |
| US20080158778A1 (en) * | 1999-06-11 | 2008-07-03 | Lipka Stephen M | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN101049924A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for producing Nano carbon tube clad by metallic sulfide |
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| CN102760877A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Transition metal sulfide/graphene composite material, and preparation method and application thereof |
| CN102903541A (en) * | 2012-10-16 | 2013-01-30 | 湖南大学 | Method for preparing graphene-based electrode material for super-capacitor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807404A (en) * | 2017-02-07 | 2017-06-09 | 合肥工业大学 | A kind of preparation method and applications of base metal base carbon coating nickel sulfide photochemical catalyst |
| CN106807404B (en) * | 2017-02-07 | 2019-07-19 | 合肥工业大学 | A kind of preparation method and applications of base metal base carbon coating nickel sulfide photochemical catalyst |
| CN108390044A (en) * | 2018-03-08 | 2018-08-10 | 湖南大学 | A kind of curing nickel-carbon composite and its preparation method and application |
| CN108390044B (en) * | 2018-03-08 | 2020-06-26 | 湖南大学 | Nickel disulfide-carbon composite material and preparation method and application thereof |
| CN108597893A (en) * | 2018-05-28 | 2018-09-28 | 江苏大学 | A kind of preparation method based on the composite electrode material for super capacitor in nickel foam |
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